US2011673A - Process for the manufacture of new conversion products from natural resins and esters thereof - Google Patents
Process for the manufacture of new conversion products from natural resins and esters thereof Download PDFInfo
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- US2011673A US2011673A US601039A US60103932A US2011673A US 2011673 A US2011673 A US 2011673A US 601039 A US601039 A US 601039A US 60103932 A US60103932 A US 60103932A US 2011673 A US2011673 A US 2011673A
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- 239000000025 natural resin Substances 0.000 title description 20
- 150000002148 esters Chemical class 0.000 title description 15
- 239000012084 conversion product Substances 0.000 title description 11
- 238000000034 method Methods 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 title description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 239000002253 acid Substances 0.000 description 35
- 229910015900 BF3 Inorganic materials 0.000 description 31
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 31
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 13
- 229910052740 iodine Inorganic materials 0.000 description 13
- 239000011630 iodine Substances 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- 235000011187 glycerol Nutrition 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- -1 for example Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- 235000005985 organic acids Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920000175 Pistacia lentiscus Polymers 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004859 Copal Substances 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 241000782205 Guibourtia conjugata Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 240000008548 Shorea javanica Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- 101100489581 Caenorhabditis elegans par-5 gene Proteins 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001589 annite Inorganic materials 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000286 fullers earth Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
Definitions
- the new reaction products are distinguished from the starting materials by a much reduced iodine value, a higher molecular weight, a somewhat smaller acid value, and a higher softening point. Moreover they do not give the Storch-Morawski color reaction, that is to say, the addition of acetic anhydride and concentrated sulphuric acid does not. produce the violet coloration characteristic of natural resins.
- the acid natural resins and esters thereof which are suitable for the manufacture of conversion products in accordance with the present invention, the following may be specially mentioned:colophony, pine resin, Batavian damar. gum mastic, copal, as well as esters of these acid resins with ethyl alcohol, dodecyl alcohol, glycol, glycerine, mannite, phenol and the like.
- the mixed esters known under the name of alkyd resins and containing the residue of an acid from a natural resin besides the residue of a polyvalent alcohol and a polybasic acid, are well adapted for the manufacture of the new conversion products.
- alkyd resins may be mentioned the condensation products, obtainable from glycerine, glycol, poly glycols or poly glycerines, pentaerythrite, m'annite. sorbite and the like by simultaneous or successive esteriflcation with colophony, pine resin,
- copal gum mastic, damar and the like and a polybasic acid, such as phthalic acid, trimellitic acid, succinic acid, maleic acid and the like.
- the volatile, halogen-containing substances which are employed in accordance with my invention are boron fluoride and complex compounds of boron fluoride with organic acids; such as, for example, acetato-fluoro-boric acid, formiatofl oro-boric acid, etc. These substances are prefer bly used in a practically anhydrous condition.
- solvents preferably those are fo nd appropriate which in themselves do not undergo a chemical change under the reaction conditions, such as for example, carbon tetrachloride, carbon disulphide etc; Furthermore ligroin, gasoline, tetraline and the like are suitable as solvents for the purpose of this invention.
- the temperature during the reaction mayvary according to the conditions. I have obtained good results with temperatures above 0 C., more par- 5 ticularly with temperatures ranging from about 0 C. to about 250 C.
- the conversion products obtainable in accordance with the present invention by condensing acid natural resins by means of the above mentioned volatile, halogen-containing substances are capable of being esterified due to the presence of free carboxylic acid groups, e. g. by means of alcohols, such as for example, ethyl alcohol, glycol, glycerine, glycol monoethylether, polyglycol, mannite, sorbite, phenol etc.
- alcohols such as for example, ethyl alcohol, glycol, glycerine, glycol monoethylether, polyglycol, mannite, sorbite, phenol etc.
- Example 1 28-29 parts by weight of boron fluoride are led into a mixture of 300 parts by weight of colophony (acid value 162, iodine value 170, saponiflcation value 180, softening point 69 C., molecular weight 500) and 400 parts by weight of carbon tetrachloride during 33-35 hours at 10-11 C. with good stirring by means of a moderately fastcurrent of nitrogen.
- colophony acid value 162, iodine value 170, saponiflcation value 180, softening point 69 C., molecular weight 500
- a dark brownish red viscous mass is gradually 30 produced, which, after 50 hours, is freed from unaltered carbon tetrachloride by steam distillation. A yellowish residue is thus obtained, which is repeatedly washed with water and after melting yields a completely clear, honey-yellow resin possessing the following constants: 35 Acid value 126 Iodine value 52.3 Saponiflcation value 1. 143 Softening point 89 C. 40 Molecular weight 680 Other solvents, such as carbon disulphide or hydrocarbons can be employed instead of carbon tetrachloride.
- Example 2 are dissolved in 150 parts by weight of benzene.
- Example 5 10 parts by weight of. boron fluoride are introduced in the course of with vigorous stirring 11 hours at about C; into a solution of 300 parts by weight of colophony glycerine ester (acid value 20, softening point 72 C.) in 150 parts by weight I of benzene. Then 300 parts by weight of benzene, 40 parts by weight of calcium oxide and 30 parts by weight of fullers earth are added. After stirring for about '1 hour the mixture is filtered and the solvent is'distilled off under diminished pressure. 295 parts by weight of a bright clear resin possessing the following constants'are ob tained: I Acid value t 18 Softening point 102-193 C.
- Example 6 10 parts by weight of boron fluoride contained in a 25% solution of boron fluoride intechnical crude benzene are introduced at 20 C. in the course of 24 hours with vigorous stirring by means of a rapid current of nitrogen into a solution of 150 parts by weight of colophony glycerine ester (softening point 0., acid value 20, iodine value 120) in 50 parts by weight of solvent naphtha.
- Example 8 20 parts by weight of boron fluoride are passed at 16-20" C. into a solution of 200 parts by weight of mastic glycerine ester (acid value 14.8, saponiflcation value 110, iodine value 113, softening point IS-77 C.) in 200 parts by weight of benzene. After 60 hours the resulting reaction product is decomposed with water and washed. After melting a clear resin possessing the following constants is obtained:
- Example 9 I 150 parts by weight of colophony glycol ester (acid value 27.3, saponiflcation value 143, iodine value 125, acetyl value 15.7, softening point 49-50 C.) are dissolved in 150 parts by weight of benzene. About 15 parts of boron fluoride are passed into this solution at 10-20 C. After standing at room temperature for about 24 hours the reaction mass no longer gives the Storch-Morawski reaction. After washing and melting the resin formed possesses the following constants:
- a conversion product of an acid,natural resin obtainable by reacting with a volatile, halogencontaining substance of the group consisting of boron fluoride and complex compounds of boron fluoride with organic acids upon an acid, natural resin.
- a conversion product of an acid, natural resin obtainable by reacting with boron fluoride upon an acid, natural resin.
- a conversion product of colophony obtainable by reacting with boron fluoride upon colophony in the presence of carbon tetrachloride at a temperature of about 10 C.
- a conversion product of an ester of an acid, natural resin obtainable by reacting with a volatile, halogen-containing substance of the group consisting of boron fluoride and complex com- .
- boron fluoride a volatile, halogen-containing substance of the group consisting of boron fluoride and complex com- .
- a conversion product of an ester of an acld, natural resin obtainable by reacting with boron fluoride upon an ester of an acid, natural resin.
- a conversion product of colophony glycerine ester obtainable by reacting with boron fluoride upon colophony glycerine ester in the presence of benzene ata temperature of about 55 C.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Aug. 20, 1935 UNlTED STATES PROCESS FOR THE MANUFACTURE OF NEW CONVERSION PRODUCTS FROM NATURAL RESINS AND ESTERS THEREOF Josef Binapfl, Crefeld, Germany, assignor to I. G.
Farbenindustrie Aktien on-the-Main, Germany gesellschaft, Frankfort- No Drawing. Application March 24, 1932, Serial No. 601,039. In Germany April 4, 1931 16 Claims. (01. 134-26) version products difier to a far reaching extent in their chemical and physical behaviour from the starting material. Instead of the acid resins or esters thereof the resin acids isolated from the same, or the esters of these resin acids can likewise be employed.
In particular, the new reaction products are distinguished from the starting materials by a much reduced iodine value, a higher molecular weight, a somewhat smaller acid value, and a higher softening point. Moreover they do not give the Storch-Morawski color reaction, that is to say, the addition of acetic anhydride and concentrated sulphuric acid does not. produce the violet coloration characteristic of natural resins.
Among the acid natural resins and esters thereof, which are suitable for the manufacture of conversion products in accordance with the present invention, the following may be specially mentioned:colophony, pine resin, Batavian damar. gum mastic, copal, as well as esters of these acid resins with ethyl alcohol, dodecyl alcohol, glycol, glycerine, mannite, phenol and the like. In addition the mixed esters, known under the name of alkyd resins and containing the residue of an acid from a natural resin besides the residue of a polyvalent alcohol and a polybasic acid, are well adapted for the manufacture of the new conversion products. As examples of the said alkyd resins may be mentioned the condensation products, obtainable from glycerine, glycol, poly glycols or poly glycerines, pentaerythrite, m'annite. sorbite and the like by simultaneous or successive esteriflcation with colophony, pine resin,
copal, gum mastic, damar and the like and a polybasic acid, such as phthalic acid, trimellitic acid, succinic acid, maleic acid and the like.
The volatile, halogen-containing substances which are employed in accordance with my invention are boron fluoride and complex compounds of boron fluoride with organic acids; such as, for example, acetato-fluoro-boric acid, formiatofl oro-boric acid, etc. These substances are prefer bly used in a practically anhydrous condition.
When employing solvents preferably those are fo nd appropriate which in themselves do not undergo a chemical change under the reaction conditions, such as for example, carbon tetrachloride, carbon disulphide etc; Furthermore ligroin, gasoline, tetraline and the like are suitable as solvents for the purpose of this invention.
The temperature during the reaction mayvary according to the conditions. I have obtained good results with temperatures above 0 C., more par- 5 ticularly with temperatures ranging from about 0 C. to about 250 C.
It is worth mentioning that the conversion products obtainable in accordance with the present invention by condensing acid natural resins by means of the above mentioned volatile, halogen-containing substances are capable of being esterified due to the presence of free carboxylic acid groups, e. g. by means of alcohols, such as for example, ethyl alcohol, glycol, glycerine, glycol monoethylether, polyglycol, mannite, sorbite, phenol etc.
The following examples will 'serve to illustrate the invention:
Example 1 28-29 parts by weight of boron fluoride are led into a mixture of 300 parts by weight of colophony (acid value 162, iodine value 170, saponiflcation value 180, softening point 69 C., molecular weight 500) and 400 parts by weight of carbon tetrachloride during 33-35 hours at 10-11 C. with good stirring by means of a moderately fastcurrent of nitrogen. I
A dark brownish red viscous mass is gradually 30 produced, which, after 50 hours, is freed from unaltered carbon tetrachloride by steam distillation. A yellowish residue is thus obtained, which is repeatedly washed with water and after melting yields a completely clear, honey-yellow resin possessing the following constants: 35 Acid value 126 Iodine value 52.3 Saponiflcation value 1. 143 Softening point 89 C. 40 Molecular weight 680 Other solvents, such as carbon disulphide or hydrocarbons can be employed instead of carbon tetrachloride.
Example 2 are dissolved in 150 parts by weight of benzene.
About 40 parts by weight of boron fluoride are added to this mixture with good cooling. After about hours the resulting addition compound is decomposed by means of water and the solvent then. removed by steam. The resin is washed again and then melted. A dark yellow resin possessing the followinggconstants is thus obtained:
Acid value 27.4 Saponification value 42 Iodine value 38.7 Acetyl value -1 -I 36 Softening point Example 3 About 27 parts by weight of gaseous boron fluoride are passed with good stirring at 10-20 C. into a solution of 280 parts by weight of gum mastic (acid value 56.3, saponiflcation value 93.1,
iodine value 45.5, acetyl value 49.8, softening point 62-64 C.) in 200 parts by weight of benzene. After about 60 hours the resulting addition compound is decomposed with'water and the solvent thenv removed by means'of steam. After again washing the resin is melted. A dark yellow resin possessing the following constants is obtained:
Acid value 39.7 Saponification value 74.3 Iodine value 26.3 Acetyl value 20.2 Softening point Example 4 I 300 parts by weight of colophony are dissolved in 150 parts by weight of benzene. About 48 parts by weight of acetato-fluoro-boric acid are added to this solutionduring 3 hours at 15-50 C. After about 12 hours the solution is'diluted with 200 parts by weight of benzene; then 240 parts by weight of calcium oxide are added. The mixture thus obtained is stirred for about 20 minutes. After filtering the mixture the solvent is distilled oif. 290 parts by weightof a clear, bright, yellow resin are obtained, possessing the following con-i -stants:
Acid value 129 Iodine value 64 Softening point 94 95 C.
Example 5 10 parts by weight of. boron fluoride are introduced in the course of with vigorous stirring 11 hours at about C; into a solution of 300 parts by weight of colophony glycerine ester (acid value 20, softening point 72 C.) in 150 parts by weight I of benzene. Then 300 parts by weight of benzene, 40 parts by weight of calcium oxide and 30 parts by weight of fullers earth are added. After stirring for about '1 hour the mixture is filtered and the solvent is'distilled off under diminished pressure. 295 parts by weight of a bright clear resin possessing the following constants'are ob tained: I Acid value t 18 Softening point 102-193 C.
Example 6 10 parts by weight of boron fluoride contained in a 25% solution of boron fluoride intechnical crude benzene are introduced at 20 C. in the course of 24 hours with vigorous stirring by means of a rapid current of nitrogen into a solution of 150 parts by weight of colophony glycerine ester (softening point 0., acid value 20, iodine value 120) in 50 parts by weight of solvent naphtha.
A dark brownish red viscous mass is gradually produced, which after 30 hours is freed from the solvent naphtha by-steam distillation. After melting a clear resin is obtained, which no longer 300 parts by weight glycerine and 296 gives the Storch-Morawski reaction. It possesses the following constants:
Iodine v 5a Acid value 36 Softening point 98-99" C.
Example 7 of a condensation product (softening point 98 C.) obtained from 640 parts by weight of colophony, 216 parts by weight of parts by weight of phthalic anhydride are dissolved in 300 parts by weight of benzene. About 40 parts by weight of boron fluoride are added to this solution, which becomes dark in color. After standing for about 50 hours at room temperature the reaction mass no longer gives the Storch-Morawski reaction. {The solvent is blown off by means of steam and the resinous residue washed with water till the washings no longer show an acidreaction. After melting in a current of nitrogen a clear resin (softening point C.) is obtained.
Example 8 20 parts by weight of boron fluoride are passed at 16-20" C. into a solution of 200 parts by weight of mastic glycerine ester (acid value 14.8, saponiflcation value 110, iodine value 113, softening point IS-77 C.) in 200 parts by weight of benzene. After 60 hours the resulting reaction product is decomposed with water and washed. After melting a clear resin possessing the following constants is obtained:
Acid value 16.4 Saponification value 11'7 Iodine value 98.5 Softening point "1... 113-114 C.
Example 9 I 150 parts by weight of colophony glycol ester (acid value 27.3, saponiflcation value 143, iodine value 125, acetyl value 15.7, softening point 49-50 C.) are dissolved in 150 parts by weight of benzene. About 15 parts of boron fluoride are passed into this solution at 10-20 C. After standing at room temperature for about 24 hours the reaction mass no longer gives the Storch-Morawski reaction. After washing and melting the resin formed possesses the following constants:
Acid val 28.8 Saponiflcation value Acetyl val 25 Iodine value 91 Softening point 78-82' C.
I claim:
1. The process which comprises reactin'g'with a volatile, halogen-containing substance of the group consisting of boron fluoride and complex compounds of boron fluoride with organic acids 3 upon material selected from ,the group consisting of acid, natural resins and esters of acid, natural group consisting of boron fluoride and complex compounds of boron fluoride with organic acids upon an acid, natural resin in the presence of a solvent therefor.
5. The process which comprises reacting with boron fluoride upon an acid, natural resin in the presence of a solvent therefor.
6. The process which comprises reacting with boron fluoride upon colophony in the presence of carbon tetrachloride at a temperature of about 10 C.
7. A conversion product of an acid,natural resin obtainable by reacting with a volatile, halogencontaining substance of the group consisting of boron fluoride and complex compounds of boron fluoride with organic acids upon an acid, natural resin.
8. A conversion product of an acid, natural resin obtainable by reacting with boron fluoride upon an acid, natural resin.
9. A conversion product of colophony obtainable by reacting with boron fluoride upon colophony in the presence of carbon tetrachloride at a temperature of about 10 C.
10. The process which comprises reacting with a volatile, halogen-containing substance of the group consisting of boron fluoride and complex compounds of boron fluoride with organic acids upon an ester of an acid, natural resin.
11. The process which comprises reacting with a volatile, halogen-containing substance of the group consisting of boron fluoride and complex compounds of boron fluoride with organic acids upon an ester of an acid, natural resin in the presence of a solvent therefor.
12. The process which comprises reacting with boron fluoride upon an ester of an acid, natural resin in the presence of a solvent therefor.
13. The process which comprises reacting with boron fluoride upon colophony glycerine ester in the presence of benzene at a temperature of about 55 C.
14. A conversion product of an ester of an acid, natural resin obtainable by reacting with a volatile, halogen-containing substance of the group consisting of boron fluoride and complex com- .pounds of boron fluoride with organic acids upon an ester of an acid, natural resin.
15. A conversion product of an ester of an acld, natural resin obtainable by reacting with boron fluoride upon an ester of an acid, natural resin.
16. A conversion product of colophony glycerine ester obtainable by reacting with boron fluoride upon colophony glycerine ester in the presence of benzene ata temperature of about 55 C.
J OSEF BINAPFL.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2011673X | 1931-04-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2011673A true US2011673A (en) | 1935-08-20 |
Family
ID=7962767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US601039A Expired - Lifetime US2011673A (en) | 1931-04-04 | 1932-03-24 | Process for the manufacture of new conversion products from natural resins and esters thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2011673A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2440242A (en) * | 1942-10-12 | 1948-04-27 | Auer Laszlo | Esterified rosin modified with organic acids and process for making same |
| US20110092667A1 (en) * | 2007-09-20 | 2011-04-21 | John Hazen | Waterbased dimerized rosins and the process to make them |
-
1932
- 1932-03-24 US US601039A patent/US2011673A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2440242A (en) * | 1942-10-12 | 1948-04-27 | Auer Laszlo | Esterified rosin modified with organic acids and process for making same |
| US20110092667A1 (en) * | 2007-09-20 | 2011-04-21 | John Hazen | Waterbased dimerized rosins and the process to make them |
| US8557954B2 (en) * | 2007-09-20 | 2013-10-15 | Lawter, Inc. | Waterbased dimerized rosins and the process to make them |
| US9012601B2 (en) | 2007-09-20 | 2015-04-21 | Lawter, Inc. | Waterbased dimerized rosins and the process to make them |
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